Lubricating compositions containing isoprene based components

ABSTRACT

A lubricating composition comprising a base oil of lubricating viscosity and one or more lubricant additives, wherein the base oil comprises or consists of a base stock which comprises or consists of at least one isoprenoid compound comprising: (i) one or two oxygen-containing moieties independently selected from ether and ester moieties; (ii) a first acyclic isoprenoid moiety containing 1 to 5 isoprenyl units; and (iii) optionally, a second acyclic isoprenoid moiety containing 1 to 5 isoprenyl units with the proviso that at least one isoprenoid moiety contains 3 to 5 isoprenyl units where the isoprenoid compound contains a single ether moiety.

The present invention relates in general to lubricating compositions. Inparticular, the present invention provides lubricating compositions,base oils and base stocks and methods of preparing and using thelubricating compositions.

Lubricating compositions generally comprise a base oil of lubricatingviscosity together with one or more additives to deliver propertiesincluding for example, reduced friction and wear, improved viscosityindex, detergency, and resistance to oxidation and corrosion. Alubricant base oil may comprise one or more sources of lubricating oil,referred to as base stocks.

Lubricant base stocks used in automotive engine lubricants are generallyobtained from petrochemical sources, for example as the higher boilingfractions isolated during the refining of crude oil or as the productsof chemical reactions of feedstocks from petrochemical sources.Lubricant base stocks can also be made from Fischer-Tropsch wax.

Lubricant base stocks may be classified as Group I, II, III, IV and Vbase stocks according to API standard 1509, “ENGINE OIL LICENSING ANDCERTIFICATION SYSTEM”, September 2012 version 17^(th) edition AppendixE, as set out in Table 1.

TABLE 1 Saturated Sulphur content hydrocarbon (% by weight) Viscositycontent ASTM D2622 Index (% by weight) or D4294 or ASTM Group ASTM D2007D4927 or D3120 D2270 I <90 and/ >0.03 and ≧80 and or <120 II ≧90 and≦0.03 and ≧80 and <120 III ≧90 and ≦0.03 and ≧120 IV polyalphaolefins Vall base stocks not in Groups I, II, III or IV

Group I, Group II and Group III base stocks are generally derived frommineral oils. Group I base stocks are typically manufactured by knownprocesses comprising solvent extraction and solvent dewaxing, or solventextraction and catalytic dewaxing. Group II and Group III base stocksare typically manufactured by known processes comprising catalytichydrogenation and/or catalytic hydrocracking, and catalytichydroisomerisation. Group IV base stocks include for example,hydrogenated oligomers of alpha olefins. Suitable processes for thepreparation of the oligomers include for example, free radicalprocesses, Zeigler catalysed processes and cationic Friedel-Craftscatalysed processes. Suitably, polyalphaolefin base stocks are derivedfor example from C₈, C₁₀, C₁₂, C₁₄ olefins and mixtures of one or morethereof.

In recent years, there has been an increased focus on identifyingsustainable replacements for products that have historically beenobtained from fossil sources. Bio-derived materials (sometimes alsocalled biobased materials) can play an important role in futurelubricant formulations, both in meeting customer demand for “green”products and in reducing dependence on non-renewable resources forexample crude oil.

Lubricant base stocks have been obtained from vegetable sources,generally as triglyceride esters of fatty acids, such as palm oil,sunflower oil and rapeseed oil. Free fatty acids from vegetable andanimal sources may also be used in the preparation of various syntheticester base stocks.

US2007/0281873 relates to a lubricating oil composition for fluiddynamic bearings which comprises 50 to 100% by mass of an ether compoundcomprising at least one ether bond and having 11 to 34 carbon atoms as abase oil and has a kinematic viscosity of at least 2.2 mm²/s at 100° C.

The use of six percent of lithium stearate in dihydrocitronellyl etherto form a grease is described by Pethrick S A and Wood H S in “Greasesfor Use over the Temperature Range −65° C. to +100° C.” SelectedGovernment Research Reports (Great Britain Ministry of Supply),Lubricants and Lubrication (1952), Volume 11 Report. No. 2, 11-20. Onpage 16 of the Report it is stated:

“In research work on synthetic hydraulic oils, workers in the FaradayLaboratory of the Royal Institution discovered that dihydrocitronellylether has a low freezing point combined with low viscosity. A pintsample of this material was made by a manufacturer and a few preliminaryexperiments were made on the utility of this ether for grease making.Six percent of lithium stearate in the ether formed a grease which whenapplied to a bearing allowed the latter to be rotated with ease at −70°C. Some bleeding occurred with this grease on storage for two months,but it is anticipated that this could be obviated by compounding withaluminium stearate in addition to the lithium stearate. The volatilityof this ether is approximately the same as that of oil to specificationD.T.D.44D when tested by I.P. method 46/42, so that no trouble due toevaporation would be expected from a grease made from this material.”

A dihydrocitronellyl moiety contains two isoprenyl units.

Benemann, J. R. et. Al. in “Chemicals From Salt Loving (Halophilic)Microbes” Final Report, National Science Foundation NSF/CPE-82006 May1982 states in its abstract: “The possibility of producing specialtychemicals—specifically diphytanyl glycerol ether (DPGE), a potentiallubricating agent, was examined . . . ”. In the conclusion it is stated:“The results obtained during this investigation do not support thepremise that lipids from Halobacteria can be economically produced. Theyields obtained were very low under all conditions tested; recoveriesfor DPGE were even lower than those reported in the literature . . .Glycerol ethers, if useful as specialty lubricants would be more easilysynthesized chemically.”

There remains a need in the art to identify new renewable sources oflubricant base stocks. In particular, there remains a need in the artfor high performance lubricating oil compositions which contain basestock which may be bio-derived (also called biobased), at least in part.

The present invention is based at least in part on the identification ofisoprenoid compounds as a source (for example, a biological source) ofcompounds which are suitable for use as components of lubricatingcompositions, and particularly as a source of base stocks forlubricating oil compositions and components thereof. Isoprenoids aremembers of a large class of organic compounds that are produced by awide variety of organisms. Isoprenoids comprise isoprenyl units whichare based upon isoprene. Isoprene has the formula:

Isoprenyl units may be arranged head-to-tail to form chains, or may bearranged to form various ring structures.

Accordingly, in a first aspect, the present invention provides alubricating composition comprising a base oil of lubricating viscosityand one or more lubricant additives, wherein the base oil comprises orconsists of a base stock which comprises or consists of at least oneisoprenoid compound comprising:

-   -   (i) one or two oxygen-containing moieties independently selected        from ether and ester moieties;    -   (ii) a first acyclic isoprenoid moiety containing 1 to 5        isoprenyl units; and    -   (iii) optionally, a second acyclic isoprenoid moiety containing        1 to 5 isoprenyl units with the proviso that at least one        isoprenoid moiety contains 3 to 5 isoprenyl units where the        isoprenoid compound contains a single ether moiety.

These and other examples of the disclosure have an advantage that basestocks for the lubricating compositions of the invention may besynthesised, at least in part, from bio-derived feedstocks (also calledbiobased feedstocks) for example via synthetic methods that are amenableto scale up. The base stocks have also been found to exhibit a range ofdesirable lubricant properties, for example, when formulated intolubricating compositions, including viscometric properties and/oroxidative stability. Accordingly, the present invention provides atleast an attractive alternative to lubricant base stocks that havepreviously been reported in the art.

For the purposes of the present invention, the following terms as usedherein shall, unless otherwise indicated, be understood to have thefollowing meanings:

The term “hydrocarbyl” as used herein refers to a group consistingexclusively of hydrogen and carbon atoms, the group containing from 1 to30 carbon atoms. Examples of hydrocarbyl groups include hydrocarbylgroups containing from 1 to 20 carbon atoms, e.g. from 1 to 12 carbonatoms, e.g. from 1 to 10 carbon atoms. Examples of hydrocarbyl groupsinclude acyclic groups, cyclic groups and groups comprising both anacyclic portion and a cyclic portion. Examples of hydrocarbyl groupsinclude linear groups and branched groups. The term “hydrocarbyl”includes monovalent groups and polyvalent groups as specified. Examplesof monovalent hydrocarbyl groups include alkyl, alkenyl, alkynyl,carbocyclyl (e.g. cycloalkyl, cycloalkenyl or aryl) and aralkyl.

The term “alkyl” as used herein refers to a monovalent straight orbranched chain alkyl moiety containing from 1 to 30 carbon atoms.Examples of alkyl groups include alkyl groups containing from 1 to 20carbon atoms, e.g. from 1 to 12 carbon atoms, e.g. from 1 to 10 carbonatoms. Particular examples include alkyl groups containing 1, 2, 3, 4, 5or 6 carbon atoms. Examples of alkyl groups include methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl andthe like.

The term “cycloalkyl” as used herein refers to a monovalent saturatedaliphatic hydrocarbyl moiety containing from 3 to 20 carbon atoms andcontaining at least one ring, wherein said ring has at least 3 ringcarbon atoms. Examples of cycloalkyl groups include cycloalkyl groupscontaining from 3 to 16 carbon atoms, e.g. from 3 to 10 carbon atoms.Particular examples include cycloalkyl groups containing 3, 4, 5 or 6ring carbon atoms. Examples of cycloalkyl groups include groups that aremonocyclic, polycyclic (e.g. bicyclic) or bridged ring system. Examplesof cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and the like. The term “cycloalkylene” as used herein refersto a corresponding divalent moiety.

The term “alkenyl” as used herein refers to a monovalent straight orbranched chain alkyl group containing from 2 to 30 carbon atoms andcontaining, in addition, at least one carbon-carbon double bond, ofeither E or Z configuration unless specified. Examples of alkenyl groupsinclude alkenyl groups containing from 2 to 20 carbon atoms, e.g. from 2to 12 carbon atoms, e.g. from 2 to 10 carbon atoms. Particular examplesinclude alkenyl groups containing 2, 3, 4, 5 or 6 carbon atoms. Examplesof alkenyl groups include ethenyl, 2-propenyl, 1-butenyl, 2-butenyl,3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-hexenyl, 2-hexenyl,3-hexenyl and the like.

The term “aryl” as used herein refers to an aromatic carbocyclic ringsystem containing from 6 to 14 ring carbon atoms. Examples of arylgroups include aryl groups containing from 6 to 10 ring carbon atoms,e.g. 6 ring carbon atoms. An example of an aryl group includes a groupthat is a monocyclic aromatic ring system or a polycyclic ring systemcontaining two or more rings, at least one of which is aromatic.Examples of aryl groups include aryl groups that comprise from 1 to 6exocyclic carbon atoms in addition to ring carbon atoms. Examples ofaryl groups include aryl groups that are monovalent or polyvalent asappropriate. Examples of monovalent aryl groups include phenyl, benzylnaphthyl, fluorenyl, azulenyl, indenyl, anthryl and the like. An exampleof a divalent aryl group is 1,4-phenylene.

The term “alkylene” refers to a divalent straight or branched chainsaturated hydrocarbyl group containing from 1 to 30 carbon atoms.Examples of alkylene groups include alkylene groups that contain from 1to 20 carbon atoms, e.g. from 1 to 12 carbon atoms, e.g. from 1 to 10carbon atoms. Particular examples include alkylene groups that contain1, 2, 3, 4, 5 or 6 carbon atoms.

The term “alkenylene” refers to a divalent straight or branched chainsaturated hydrocarbyl group containing from 2 to 30 carbon atoms andcontaining, in addition, at least one carbon-carbon double bond, ofeither E or Z configuration unless specified. Examples of alkenylenegroups include alkenylene groups that contain from 2 to 20 carbon atoms,e.g. from 2 to 12 carbon atoms, e.g. from 2 to 10 carbon atoms.Particular examples include alkenylene groups that contain 2, 3, 4, 5 or6 carbon atoms.

The term “alkoxy” as used herein refers to —O-alkyl, wherein alkyl is asdefined herein. In some examples an alkoxy group contains from 1 to 30carbon atoms, e.g. from 1 to 26 carbon atoms, or from 1 to 20 carbonatoms, or from 1 to 12 carbon atoms e.g. from 1 to 10 carbon atoms.Particular examples include alkoxy groups that contain 1, 2, 3, 4, 5 or6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy,propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.

The term “acyloxy” as used herein refers to —OC(O)-alkyl or —OC(O)-aryl,wherein alkyl and aryl are as defined herein. Examples of acyloxy groupsinclude acyloxy groups that contain from 2 to 20 carbon atoms, e.g. from2 to 12 carbon atoms, e.g. from 2 to 10 carbon atoms. Particularexamples include alkoxy groups that contain 2, 3, 4, 5, 6 or 7 carbonatoms. Examples of acyloxy groups include acetoxy, propoxy, isopropoxy,benzoyloxy and the like.

The term “heterocyclyl” as used herein refers to a saturated (e.g.heterocycloalkyl) or unsaturated (e.g. heteroaryl) heterocyclic ringmoiety containing from 3 to 14 ring atoms, wherein said ring atomsinclude at least one ring carbon atom and at least one ring heteroatomselected from nitrogen, oxygen and sulphur. Examples of heterocyclylgroups include heterocyclyl groups that contain from 3 to 10 ring atoms,e.g. from 3 to 6 ring atoms. Particular examples include heterocyclylgroups that contain 5 or 6 ring atoms, including for example, groupsthat are saturated, unsaturated or aromatic. Examples of heterocyclylgroups include heterocyclyl groups that, in addition to ring carbonatoms, comprise from 1 to 6 exocyclic carbon atoms. Examples ofheterocyclyl groups include those that are monovalent or polyvalent asappropriate.

The term “heteroaryl” as used herein refers to an aromatic heterocyclicring system containing from 5 to 14 ring atoms, wherein said ring atomsinclude at least one ring carbon atoms and at least one ring heteroatomselected from nitrogen, oxygen and sulphur. Examples of heteroarylgroups include heteroaryl groups that are a monocyclic ring system or apolycyclic (e.g. bicyclic) ring system, containing two or more rings, atleast one of which is aromatic. Examples of heteroaryl groups includethose that, in addition to ring carbon atoms, comprise from 1 to 6exocyclic carbon atoms. Examples of heteroaryl groups include those thatare monovalent or polyvalent as appropriate. Examples of heteroarylgroups include furanyl, and benzo[b]furanyl groups.

The term “optionally substituted” as used herein means unsubstituted orsubstituted. The term “substituted” as used herein as used in connectionwith a chemical group means that one or more (e.g. 1, 2, 3, 4 or 5) ofthe hydrogen atoms in that group are replaced independently of eachother by a corresponding number of substituents. When present, the oneor more substituents are present only at positions where they arechemically possible, i.e. that any substitution is in accordance withpermitted valence of the substituted atom and the substituent and thatthe substitution results in a stable compound. Suitable substituentsinclude hydrocarbyl groups, including for example: methyl; ethyl;n-propyl; iso-propyl; n-butyl; iso-butyl; t-butyl; n-pentyl; neo-pentyl;3,3-dimethylpropyl; 2,3-dimethylpropyl; 2,2-dirmthylpropyl and2-ethylhexyl. Suitable substituents include groups comprisingheteroatoms including for example: nitrogen, oxygen and sulphur.

The term “isoprenoid” as used herein refers to a monovalent or divalentacyclic hydrocarbyl moiety that is an oligomer of isoprene. Compoundscontaining isoprenoid moieties are referred to herein as “isoprenoidcompounds”. The isoprenyl units, for example —[CH₂CH═C(CH₃)CH₂]— and—[CH₂CH₂CH(CH₃)CH₂]— may be connected head to tail and/or head to headin regular or random order.

Unless specified otherwise, the isoprenoid moiety contains from 1 to 5isoprenyl units, e.g. 2 to 5 isoprenyl units, e.g. 3 to 5 isoprenylunits, e.g. 3 or 4 isoprenyl units, e.g. 3 isoprenyl units.

In at least some examples, the isoprenoid moieties are derived fromfarnesene or farnesol or combinations thereof. In at least someexamples, the isoprenoid compounds are derived from farnesene orfarnesol or combinations thereof.

In at least some examples the isoprenoid moiety is derived frombio-derived feedstocks (also called biobased feedstocks), including forexample farnesene and farnesol. In at least some examples the isoprenoidcompound is derived from bio-derived feedstocks (also called biobasedfeedstocks), including for example farnesene and farnesol.

Suitably, the isoprenoid moiety is derived from farnesene. Suitably, theisoprenoid compound is derived from farnesene. Farnesene is anisoprenoid compound containing three isoprenyl units. There are sixisomers of farnesene. α-Farnesene and β-farnesene differ by the locationof one double bond. α-Farnesene is3,7,11-trimethyl-1,3,6,10-dodecatetraene and β-farnesene is7,11-dimethyl-3-methylene-1,6,10-dodecatriene. There are fourstereoisomers of α-Farnesene and two stereoisomers of β-farnesene.

Other suitable sources of isoprenoid moieties and isoprenoid compoundsinclude compounds containing two isoprenyl units. Examples of compoundscontaining two isoprenyl units include geraniol, nerol and citronellol.

Geraniol is found in rose oil, palmarosa oil and Java type citronellaoil. It also occurs in small quantities in geranium, lemon, and manyother essential oils. It may be represented by the formula:

Nerol is found in many essential oils including oils from lemongrass andhops. It is also present in neroli oil and may be represented by theformula:

Citronellol has two enantiomers which may be represented by thestructural formulae:

The (+) isomer is found in citronella oil and the (−) isomer is presentin oils of rose and Pelargonium geraniums.

In at least some examples (for example where the isoprenoid moiety isbonded to a heteroatom e.g. oxygen, sulphur or nitrogen, through aterminal carbon atom) the isoprenoid moiety is derived from farnesol. Inat least some examples (for example where the isoprenoid moiety isbonded to a heteroatom e.g. oxygen, sulphur or nitrogen, through aterminal carbon atom) the isoprenoid compound is derived from farnesol.Farnesol is a natural organic compound which is an acyclic sesquiterpenealcohol. Farnesol is an isoprenoid compound containing three isoprenylunits. Farnesol is present in many essential oils such as citronella,neroli, cyclamen, lemon grass, tuberose, rose, musk, balsam and tolu.

Suitable isoprenoid moieties include saturated and unsaturatedisoprenoid moieties. In at least some examples the isoprenoid moietiesare saturated isoprenoid moieties. In at least some examples theisoprenoid moieties are unsaturated isoprenoid moieties.

In at least some examples, the isoprenoid compound comprises:

-   -   (i) one or two oxygen-containing moieties independently selected        from ether and ester moieties;    -   (ii) a first acyclic isoprenoid moiety containing 3 to 5        isoprenyl units; and    -   (iii) optionally, a second acyclic isoprenoid moiety containing        1 to 5 isoprenyl units.

In at least some examples, the isoprenoid compound is represented by theformula (1), (2) or (3):

R¹—O-T¹  (1)

R²—C(O)O-T²  (2)

T³-O-T⁴  (3)

wherein:R¹ and R² each represent an acyclic unsubstituted hydrocarbyl group oran acyclic substituted hydrocarbyl group other than an acyclic,saturated or unsaturated, isoprenoid moiety containing from 1 to 5isoprenyl units;T¹ represents an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 3 to 5 isoprenyl units;T² represents an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 1 to 5 isoprenyl units; andT³ and T⁴ each represent an acyclic, saturated or unsaturated,isoprenoid moiety containing from 1 to 5 isoprenyl units, with theproviso that at least one of T³ and T⁴ represents an acyclic, saturatedor unsaturated, isoprenoid moiety containing from 3 to 5 isoprenylunits.

In at least some examples T¹, T², T³ each independently represents anacyclic, saturated or unsaturated, isoprenoid moiety containing 3, 4 or5 isoprenyl units, for example an acyclic, saturated or unsaturated,isoprenoid moiety containing 3 isoprenyl units. In at least someexamples, each of T¹, T² and T³ is derived from farnesene or farnesol orcombinations thereof.

In at least some further examples, the isoprenoid compound isrepresented by the formula (4), (5), (6), (7) or (8):

R³—O—R⁴—O-T⁵  (4)

T⁶-O—R⁵—O-T⁷  (5)

R⁶—O-T⁸-O—R⁷  (6)

R⁸—OC(O)—R⁹—C(O)O-T⁹  (7)

T¹⁰-OC(O)—R¹⁰—C(O)O-T¹¹  (8)

wherein:R³, R⁶, R⁷ and R⁸ each independently represent an acyclic unsubstitutedhydrocarbyl group or an acyclic substituted hydrocarbyl group other thanan acyclic, saturated or unsaturated, isoprenoid moiety containing from1 to 5 isoprenyl units;R⁴ and R⁵ each independently represent:

-   -   a divalent, cyclic or acyclic hydrocarbyl group, other than a        divalent acyclic, saturated or unsaturated, isoprenoid moiety        containing from 1 to 5 isoprenyl units;    -   or a heterocyclyl group;        R⁹ and R¹⁰ each independently represent:    -   a divalent, cyclic or acyclic hydrocarbyl group, other than a        divalent acyclic, saturated or unsaturated, isoprenoid moiety        containing from 1 to 5 isoprenyl units;    -   a heterocyclyl group; or    -   a covalent bond;        T⁸ represents a divalent acyclic, saturated or unsaturated,        isoprenoid moiety containing from 1 to 5 isoprenyl units; and        T⁵, T⁶, T⁷, T⁹, T¹⁰ and T¹¹ each independently represents an        acyclic, saturated or unsaturated, isoprenoid moiety containing        from 1 to 5 isoprenyl units.

In at least some examples T⁵, T⁶, T⁷, T⁹, T¹⁰, and T¹¹ eachindependently represents an acyclic, saturated or unsaturated,isoprenoid moiety containing 3, 4 or 5 isoprenyl units, for example anacyclic, saturated or unsaturated, isoprenoid moiety containing 3isoprenyl units. In at least some examples, each of T⁵, T⁶, T⁷, T⁹, T¹⁰,and T¹¹ is derived from farnesene or farnesol or combinations thereof.

In at least some examples T⁸ represents a divalent acyclic, saturated orunsaturated, isoprenoid moiety containing 3, 4 or 5 isoprenyl units, forexample a divalent acyclic, saturated or unsaturated, isoprenoid moietycontaining 3 isoprenyl units. In at least some examples, T⁸ is derivedfrom farnesene or farnesol or combinations thereof.

Examples of isoprenyl units include substituted isoprenyl units andunsubstituted isoprenyl units. Examples of substituted isoprenyl unitsinclude those substituted with one or two groups represented by theformula —O—R¹⁰ or the formula —OC(O)—R¹¹, wherein R¹⁰ and R¹¹ eachrepresents a hydrocarbyl group containing from 1 to 30 carbon atoms,e.g. from 1 to 26 carbon atoms or from 1 to 20 carbon atoms or from 1 to10 carbon atoms, for example, wherein R¹⁰ and R¹¹ each represents anacyclic alkyl or alkenyl group containing from 1 to 30 carbon atoms, forexample from 1 to 26 carbon atoms or from 1 to 20 carbon atoms or from 1to 10 carbon atoms.

Suitably, each isoprenyl unit is unsubstituted.

Examples of acyclic isoprenoid moieties (for example, each of T¹, T²,T³, T⁴, T⁵, T⁶, T⁷, T⁹, T¹⁰, and T¹¹, include:

[CH₂CH═C(CH₃)CH₂]_(m)H

[CH₂CH₂CH(CH₃)CH₂]_(n)H

wherein m and n are each an integer of from 1 to 5, for example 3, 4 or5, suitably 3 and

—C(CH₃)(CH═CH₂)CH₂—[CH₂CH═C(CH₃)CH₂]_(p)H

C(CH₃)(CH₂CH₃)CH₂—[CH₂CH₂CH(CH₃)CH₂]_(q)H

wherein p and q are each an integer of from 0 to 4, for example 1, 2 or3, suitably 2.

Examples of branched acyclic isoprenoid moieties (for example, each ofT¹, T², T³, T⁴, T⁵, T⁶, T⁷, T⁹, T¹⁰, and T¹¹) include:

wherein r and s are each an integer such that r+s=0, 1, 2 or 3, forexample 2 or 3 and

wherein t and u are each an integer such that t+u=0, 1, 2 or 3, forexample 2 or 3.

In at least some examples, the isoprenoid moiety is bonded to anadjacent oxygen atom via a terminal carbon atom of the isoprenoidmoiety, for example as represented by the structures:

—O—[CH₂CH═C(CH₃)CH₂]_(m′)H

—O—[CH₂CH₂CH(CH₃)CH₂]_(n′)H

wherein m′ and n′ are each an integer of from 1 to 5, for example 3, 4or 5, suitably 3 and

—O—C(CH₃)(CH═CH₂)CH₂—[CH₂CH═C(CH₃)CH₂]_(p′)H

—O—C(CH₃)(CH₂CH₃)CH₂—[CH₂CH₂CH(CH₃)CH₂]_(q′)H

wherein p′ and q′ are each an integer of from 0 to 4, for example 1, 2or 3, suitably 2.

In at least some examples, the isoprenoid moiety is bonded to anadjacent oxygen atom via a non-terminal carbon atom of the isoprenoidmoiety, for example as represented by the structures:

wherein r′ and s′ are each an integer such that r′+s′=0, 1, 2 or 3, forexample 2 or 3 and

wherein t′ and u′ are each an integer such that t+u=0, 1, 2 or 3, forexample 2 or 3.

In at least some examples the isoprenoid moiety is bonded to an adjacentoxygen atom via a primary carbon atom of the isoprenoid moiety, forexample as represented by the structures:

—O—[CH₂CH═C(CH₃)CH₂]_(m′)H

—O—[CH₂CH₂CH(CH₃)CH₂]_(n′)H

wherein m′ and n′ are each an integer of from 1 to 5, for example 3, 4or 5, suitably 3.

In at least some examples the isoprenoid moiety is bonded to an adjacentoxygen atom via a secondary carbon atom of the isoprenoid moiety, forexample as represented by the structures:

—O—C(CH₃)(CH═CH₂)CH₂—[CH₂CH═C(CH₃)CH₂]_(p′)H

—O—C(CH₃)(CH₂CH₃)CH₂—[CH₂CH₂CH(CH₃)CH₂]_(q′)H

wherein p′ and q′ are each an integer of from 0 to 4, for example 1, 2or 3, suitably 2.

In at least some examples, the isoprenoid moiety is bonded to anadjacent oxygen atom via a tertiary carbon atom of the isoprenoidmoiety, for example as represented by the structures:

wherein r′ and s′ are each an integer such that r′+s′=0, 1, 2 or 3, forexample 2 or 3 and

wherein t′ and u′ are each an integer such that t+u=0, 1, 2 or 3, forexample 2 or 3.

Examples of divalent acyclic isoprenyl moieties (for example T⁸) includedivalent acyclic, saturated or unsaturated, isoprenoid moiety containing1 to 5 isoprenyl units, for example 3 or 4 isoprenyl units, for example3 isoprenyl units. Suitably, the divalent acyclic isoprenyl unit isderived from farnesene or farnesol or combinations thereof. Examples ofdivalent acyclic isoprenyl moieties include:

—[CH₂CH₂CH(CH₃)CH₂]_(v)— and —[CH₂CH═C(CH₃)CH₂]_(w)—

wherein each of v and w is an integer of from 1 to 5, for example from 3to 5, for example 3 or 4, and suitably 3. Suitably, each divalentacyclic isoprenyl moiety (for example T⁸) is derived from farnesene orfarnesol or combinations thereof.

In at least some examples (for example T⁸), the divalent isoprenoidmoiety is bonded to at least one adjacent oxygen atom via a non-terminalcarbon atom of the divalent isoprenoid moiety. Examples of isoprenoidcompounds in which divalent isoprenoid moieties are bonded to at leastone adjacent oxygen atom via at last one non-terminal carbon atominclude those that are unsaturated with the following structuralformulae:

in which the R groups each independently represent an acyclicunsubstituted hydrocarbyl group or an acyclic substituted hydrocarbylgroup other than an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 1 to 5 isoprenyl units.

Examples of isoprenoid compounds in which divalent isoprenoid moietiesare bonded to at least one adjacent oxygen atom via at last onenon-terminal carbon atom include those that are saturated with thefollowing structural formulae:

in which the R groups each independently represent an acyclicunsubstituted hydrocarbyl group or an acyclic substituted hydrocarbylgroup other than an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 1 to 5 isoprenyl units.

In at least some examples, R¹, R³, R⁶, R⁷ and R⁸ each independentlyrepresents a C₁ to C₃₀ hydrocarbyl group (other than an acyclic,saturated or unsaturated, isoprenoid moiety containing 1 to 5 isoprenylunits), for example a C₈ to C₃₀ alkyl or alkenyl group other than anacyclic, saturated or unsaturated, isoprenoid moiety containing 1 to 5isoprenyl units, for example a C₈ to C₂₀ alkyl or alkenyl group, or aC₁₂ to C₂₀ alkyl or alkenyl group, or a C₁₂ to C₁₈ alkyl or alkenylgroup, or a C₈ to C₁₈ alkyl or alkenyl group, or a C₈ to C₁₆ alkyl oralkenyl group, or a C₈ to C₁₄ alkyl or alkenyl group other than anacyclic, saturated or unsaturated, isoprenoid moiety containing 1 to 5isoprenyl units. In at least some examples, R¹, R³, R⁶, R⁷ and R⁸ areeach independently selected from n-decyl, n-dodecyl, n-tetradecyl,n-hexadecyl, cis-9-hexadecen-1-yl, n-octadecyl, 16-methylheptadecyl,cis-9-octadecen-1-yl, and 9Z,12Z-octadecadien-1-yl. Suitably, R¹, R³,R⁶, R⁷ and R⁸ are each independently selected from decyl and tetradecyl.

In at least some examples, R¹, R³, R⁶, R⁷ and R⁸ are each independentlyderived from the corresponding fatty alcohols, for example capricalcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleylalcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol or linoleylalcohol.

In at least some examples, R² represents a C₁ to C₃₀ hydrocarbyl group(other than an acyclic, saturated or unsaturated, isoprenoid moietycontaining 1 to 5 isoprenyl units), for example a C₇ to C₂₉ alkyl oralkenyl group, or a C₇ to C₁₉ alkyl or alkenyl group, or a C₉ to C₁₉alkyl or alkenyl group, or a C₁₁ to C₁₉ alkyl or alkenyl group, or a C₁₁to C₁₇ alkyl or alkenyl group, or a C₁₃ to C₁₇ alkyl or alkenyl group,or a C₁₅ to C₁₇ alkyl or alkenyl group, other than an acyclic, saturatedor unsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units. Inat least some examples, R² is selected from n-nonyl, n-undecyl,n-tridecyl, n-pentadecyl, cis-8-pentadecen-1-yl, n-heptadecyl,15-methylhexadecyl, cis-8-heptadecen-1-yl, and8Z,11Z-heptadecadien-1-yl.

In at least some examples, the group R²—C(O)O— is derived from thecorresponding fatty acid, for example decanoic acid, dodecanoic acid,myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearicacid, oleic acid or linoleic acid.

In at least some examples, R⁴ and R⁵ each represents a divalent, cyclicor acyclic C₁ to C₃₀ hydrocarbyl group (other than an acyclic, saturatedor unsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units),for example a C₂ to C₁₀ alkylene group, a C₂ to C₁₀ alkenylene group, aC₅ to C₁₀ cycloalkylene group, a C₆ to C₁₀ aryl group, or a C₄ to C₁₀heterocyclyl group other than an acyclic, saturated or unsaturated,isoprenoid moiety containing 1 to 5 isoprenyl units. In at least someexamples, R⁴ and R⁵ each represents a C₂ to C₁₀ alkylene group, a C₂ toC₁₀ alkenylene group or a C₆ to C₁₀ aryl group other than an acyclic,saturated or unsaturated, isoprenoid moiety containing 1 to 5 isoprenylunits. In at least some examples, R⁴ and R⁵ each represents a C₂ to C₆alkylene group, a C₂ to C₆ alkenylene group or a C₆ aryl group otherthan an acyclic, saturated or unsaturated, isoprenoid moiety containing1 to 5 isoprenyl units. Examples of suitable groups includeethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, n-butane-1,2-diyl,n-butane-1,4-diyl, but-2-ene-1,4-diyl, 1,2-phenylene and 1,4-phenylene.Suitable R⁴ and R⁵ groups include ethane-1,2-diyl, 1,2-phenylene and1,4-phenylene.

In at least some examples, the —O—R⁴—O— group or —O—R⁵—O— group isderived from the corresponding diol compound. Suitable diol compoundsinclude 1,2-diols, 1,3-diols and 1,4-diols, for example, ethylene-diol,propylene-1,2-diol, propylene-1,3-diol, butylene-1,2-diol,butylene-1,3-diol, butylene-1,4-diol, 2-butene-1,4-diol,benzene-1,2-diol and hydroquinone.

In at least some examples, R⁹ and R¹⁰ each represents a divalent, cyclicor acyclic C₁ to C₃₀ hydrocarbyl group (other than an acyclic, saturatedor unsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units),for example a C₁ to C₁₀ alkylene group, a C₂ to C₁₀ alkenylene group, aC₆ to C₁₀ aryl group, a C₄ to C₁₀ heterocyclyl group, or a covalentbond, other than an acyclic, saturated or unsaturated, isoprenoid moietycontaining 1 to 5 isoprenyl units. In at least some examples, R⁹ and R¹⁰each represents a C₁ to C₄ alkylene group, a C₂ to C₄ alkenylene group,a C₆ aryl group, a C₄ to C₆ heterocyclyl group, or a covalent bond otherthan an acyclic, saturated or unsaturated, isoprenoid moiety containing1 to 5 isoprenyl units. Examples of R⁹ and R¹⁰ groups include a covalentbond, methylene, ethane-1,2-diyl, propane-1,3-diyl, n-butane-1,4-diyl,n-pentane-1,5-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene,ethene-1,2-diyl (i.e. —CH═CH—, E or Z configuration), 2,5-furandiyl and2,5-tetrahydrofurandiyl. More suitable R⁹ and R¹⁰ groups include acovalent bond, methylene, ethane-1,2-diyl, 1,2-phenylene, 1,4-phenylene,2,5-furandiyl and 2,5-tetrahydrofurandiyl. Still more suitable R⁹ andR¹⁰ groups include 2,5-furandiyl, cis 2,5-tetrahydrofurandiyl and trans2,5-tetrahydrofurandiyl. In at least some examples the isoprenoidcompounds are racemic mixtures.

In at least some examples, each of the —OC(O)—R⁹—C(O)O— group and the—OC(O)—R¹⁰—C(O)O— group is derived from the corresponding dicarboxylicacid compound, for example, oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, phthalic acid, isophthalicacid, terephthalic acid, maleic acid, fumaric acid,furan-2,5-dicarboxylic acid or tetrahydrofuran-2,5-dicarboxylic acid. Inat least some example, the dicarboxylic acids are bioderived, forexample succinic acid derived for example from fermentation of sugars.

Exemplary compounds of formula (1) include those wherein R¹ represents aC₈ to C₃₀ alkyl or alkenyl group, for example a C₈ to C₂₀ alkyl oralkenyl group other than an acyclic, saturated or unsaturated,isoprenoid moiety containing 1 to 5 isoprenyl units and T¹ represents anacyclic, saturated or unsaturated, isoprenoid moiety containing from 3to 5 isoprenyl units, for example 3 or 4 isoprenyl units and suitably 3isoprenyl units. Suitable compounds of formula (1) include those whereinR¹ is a C₁₂ to C₂₀ alkyl or alkenyl group other than an acyclic,saturated or unsaturated, isoprenoid moiety containing 1 to 5 isoprenylunits and T¹ is represented by a formula selected from—[CH₂CH₂CH(CH₃)CH₂]_(r)H and —[CH₂CH═C(CH₃)CH₂]_(r)H wherein r is aninteger of from 3 to 5, for example 3 or 4, and suitably 3 isoprenylunits, for example derived from farnesene or farnesol.

Compounds of formula (1) include those represented by the formulas (9)and (10):

wherein n is 10, 12, 14 or 16, for example wherein n is 10, 12 or 16,e.g. 10 or 12. Another example of a compound represented by formula (1)is represented by formula: (11):

Exemplary compounds of formula (2) include those wherein R² is a C₇ toC₁₉ alkyl or alkenyl group other than an acyclic, saturated orunsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units and T²represents an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 3 to 5 isoprenyl units, for example 3 or 4 isoprenylunits and suitably 3 isoprenyl units. Suitable compounds of formula (2)include those wherein R² is a C₁₁ to C₁₉ alkyl or alkenyl group otherthan an acyclic, saturated or unsaturated, isoprenoid moiety containing1 to 5 isoprenyl units and T² is represented by a formula selected from—[CH₂CH₂CH(CH₃)CH₂]_(r)H and —[CH₂CH═C(CH₃)CH₂]_(r)H wherein r is aninteger of from 3 to 5, for example 3 or 4, and suitably 3 isoprenylunits, for example derived from farnesene or farnesol.

Compounds of formula (2) include farnesyl oleate (12):

and hydrogenated farnesyl oleate.

Exemplary compounds of formula (3) include those wherein T³ and T⁴independently represent an acyclic, saturated or unsaturated, isoprenoidmoiety containing 3 to 5 isoprenyl units, for example 3 or 4 isoprenylunits and suitably 3 isoprenyl units. Suitable compounds of formula (3)include those wherein T³ and T⁴ each represent the same group selectedfrom —[CH₂CH₂CH(CH₃)CH₂]_(p)H and —[CH₂CH═C(CH₃)CH₂]_(p)H wherein p isan integer of from 3 to 5, for example 3 or 4, and suitably 3 isoprenylunits, for example derived from farnesene or farnesol.

Compounds of formula (3) include difarnesyl ether (13) and hydrogenateddifarnesyl ether (14):

Exemplary compounds of formula (4) include those wherein R⁴ represents aC₂ to C₁₀ alkylene group, a C₂ to C₁₀ alkenylene group, a C₅ to C₁₀cycloalkylene group, a C₆ to C₁₀ aryl group, or a C₄ to C₁₀ heterocyclylgroup, other than an acyclic, saturated or unsaturated, isoprenoidmoiety containing 1 to 5 isoprenyl units, for example a C₂ to C₁₀alkylene group, a C₂ to C₁₀ alkenylene group or a C₆ to C₁₀ aryl groupincluding for example a C₂ to C₆ alkylene group, a C₂ to C₆ alkenylenegroup or a C₆ aryl group other than an acyclic, saturated orunsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units.Examples of suitable groups include ethane-1,2-diyl, propane-1,2-diyl,propane-1,3-diyl, n-butane-1,2-diyl, n-butane-1,4-diyl,but-2-ene-1,4-diyl, 1,2-phenylene and 1,4-phenylene. Exemplary compoundsof formula (4) include those wherein T⁵ represents an acyclic, saturatedor unsaturated, isoprenoid moiety containing 3 to 5 isoprenyl units, forexample 3 or 4 isoprenyl units and suitably 3 isoprenyl units, forexample derived from farnesene or farnesol. Exemplary compounds offormula (4) include those represents by the formula:CH₃CH₂CH₂—O—CH₂CH(CH₃)—O-T⁵ (15)

Exemplary compounds of formula (5) include those wherein R⁵ represents aC₂ to C₁₀ alkylene group, a C₂ to C₁₀ alkenylene group, a C₅ to C₁₀cycloalkylene group, a C₆ to C₁₀ aryl group, or a C₄ to C₁₀ heterocyclylgroup, other than an acyclic, saturated or unsaturated, isoprenoidmoiety containing 1 to 5 isoprenyl units, for example a C₂ to C₁₀alkylene group, a C₂ to C₁₀ alkenylene group or a C₆ to C₁₀ aryl groupincluding for example a C₂ to C₆ alkylene group, a C₂ to C₆ alkenylenegroup or a C₆ aryl group other than an acyclic, saturated orunsaturated, isoprenoid moiety containing 1 to 5 isoprenyl units.Examples of suitable groups include ethane-1,2-diyl, propane-1,2-diyl,propane-1,3-diyl, n-butane-1,2-diyl, n-butane-1,4-diyl,but-2-ene-1,4-diyl, 1,2-phenylene and 1,4-phenylene. Exemplary compoundsof formula (5) include those wherein T⁵ and T⁶ each independentlyrepresents an acyclic, saturated or unsaturated, isoprenoid moietycontaining 3 to 5 isoprenyl units, for example 3 or 4 isoprenyl unitsand suitably 3 isoprenyl units, for example derived from farnesene orfarnesol.

Compounds of formula (5) include1,4-bis((3,7,11-trimethyldodecyl)oxy)benzene. This is represented by theformula:

Other examples of compounds of formula (5) include the compoundrepresented by the formula:

and its unsaturated analogues.

Other examples of compounds of formula (5) include compounds representedby the formula: T⁶-O—CH₂CH(CH₃)—O-T⁷ (18)

Exemplary compounds of formula (6) include those wherein R⁶ and R⁷ eachindependently represents a C₈ to C₃₀ alkyl or alkenyl group, for examplea C₈ to C₂₀ alkyl or alkenyl group, or a C₁₂ to C₂₀ alkyl or alkenylgroup, or a C₁₂ to C₁₈ alkyl or alkenyl group, or a C₈ to C₁₈ alkyl oralkenyl group, or a C₈ to C₁₆ alkyl or alkenyl group, or a C₈ to C₁₄alkyl or alkenyl group other than an acyclic, saturated or unsaturated,isoprenoid moiety containing 1 to 5 isoprenyl units and T⁸ represents adivalent acyclic, saturated or unsaturated, isoprenoid moiety containingfrom 3 to 5 isoprenyl units, for example 3 or 4 isoprenyl units andsuitably 3 isoprenyl units, for example derived from farnesene orfarnesol. Suitable compounds of formula (6) include those wherein R⁶ andR⁷ are each independently a C₈ to C₃₀ alkyl or alkenyl group other thanan acyclic, saturated or unsaturated, isoprenoid moiety containing 1 to5 isoprenyl units and T³ is represented by a formula selected from—[CH₂CH₂CH(CH₃)CH₂]_(v)— and —[CH₂CH═C(CH₃)CH₂]_(w)—wherein each of vand w is an integer of from 3 to 5, for example 3 or 4, and suitably 3.Suitably, T⁸ is derived from farnesene or farnesol.

Compounds of formula (6) include:

Exemplary compounds of formula (7) include those wherein R⁸ represents aC₈ to C₃₀ alkyl or alkenyl group, for example a C₈ to C₂₀ alkyl oralkenyl group, or a C₁₂ to C₂₀ alkyl or alkenyl group, or a C₁₂ to C₁₈alkyl or alkenyl group, or a C₈ to C₁₈ alkyl or alkenyl group, or a C₈to C₁₆ alkyl or alkenyl group, or a C₈ to C₁₄ alkyl or alkenyl groupother than an acyclic, saturated or unsaturated, isoprenoid moietycontaining 1 to 5 isoprenyl units, R⁹ represents a covalent bond, a C₁to C₁₀ alkylene group, a C₂ to C₁₀ alkenylene group, a C₆ to C₁₀ arylgroup, or a C₄ to C₁₀ heterocyclyl group, other than an acyclic,saturated or unsaturated, isoprenoid moiety containing 1 to 5 isoprenylunits and T⁹ represents an acyclic, saturated or unsaturated, isoprenoidmoiety containing from 3 to 5 isoprenyl units, suitably 3 or 4 isoprenylunits and for example 3 isoprenyl units, for example derived fromfarnesene or farnesol. Suitable compounds of formula (5) include thosewherein R⁸ is a C₁₂ to C₂₀ alkyl or alkenyl group, other than anacyclic, saturated or unsaturated, isoprenoid moiety containing 1 to 5isoprenyl units, R⁹ represents a covalent bond, C₁ to C₄ alkylene group,a C₂ to C₄ alkenylene group, a C₆ aryl group, or a C₄ to C₆ heterocyclylgroup other than an acyclic, saturated or unsaturated, isoprenoid moietycontaining 1 to 5 isoprenyl units and T⁹ has a formula selected from—[CH₂CH₂CH(CH₃)CH₂]_(r)H and —[CH₂CH═C(CH₃)CH₂]_(r)H wherein r is aninteger of from 3 to 5, suitably 3 or 4, and more suitably 3. Suitably,T⁹ is derived from farnesene or farnesol. Compounds of formula (7)include:

Exemplary compounds of formula (8) include those wherein R¹⁰ representsa covalent bond, a C₁ to C₁₀ alkylene group, a C₂ to C₁₀ alkenylenegroup, a C₆ to C₁₀ aryl group, or a C₄ to C₁₀ heterocyclyl group, otherthan an acyclic, saturated or unsaturated, isoprenoid moiety containing1 to 5 isoprenyl units and T¹⁰ and T¹¹ each independently represent anacyclic, saturated or unsaturated, isoprenoid moiety containing 1 to 5isoprenyl units, for example, 3 to 5 isoprenyl units, for example 3 or 4isoprenyl units and suitably 3 isoprenyl units, for example derived fromfarnesene or farnesol. Suitable compounds of formula (8) include thosewherein R¹⁰ represents a covalent bond, a C₁ to C₄ alkylene group, a C₂to C₄ alkenylene group, a C₆ aryl group, or a C₄ to C₆ heterocyclylgroup, and T¹⁰ and T¹¹ each represent the same group selected from—[CH₂CH₂CH(CH₃)CH₂]_(n)H and —[CH₂CH═C(CH₃)CH₂]_(m)H wherein m and n areeach an integer of from 1 to 5, for example 3, 4 or 5, suitably 3.Suitably, T¹⁰ and T¹¹ are each derived from farnesene or farnesol.

Compounds of formula (8) include difarnesyl-furan-2,5-dicarboxylate(21), hydrogenated difarnesyl-furan-2,5-dicarboxylate (22) andhydrogenated difarnesyl terephthalate (23):

In at least some examples of the present disclosure, the at least oneisoprenoid compound has a formula selected from formulae (1), (2), (3),(4), (5), (6), (7), (8) for example the at least one isoprenoid compoundhas a formula selected from formulae (9), (10), (11), (12), (13), (14),(15), (16), (17), (18), (19), (20), (21), (22) and (23) and as definedherein.

Methods for making the isoprenoid compounds as defined herein includechemical syntheses and biological syntheses and combinations thereof.Methods for making isoprenoid compounds are known in the art, forexample methods as described in U.S. Pat. No. 7,399,323. Suitably, theat least one isoprenoid compound as defined herein or precursor thereforis derived from a biological source, for example by treating a suitablefeedstock with microorganisms to produce the isoprenoid compound orprecursor therefor. Examples of suitable microorganisms include yeastsand bacteria (for example E. Coli). Examples of microorganisms includemicroorganisms adapted for example by bioengineering to produce theisoprenoid compound or precursor thereof. Examples of suitablefeedstocks include sugar(s) and glycerol. Examples of suitable sugarsinclude those available from sugar cane. Methods for converting sugarsor glycerol or combinations thereof to isoprenoid compounds includecontacting the sugar and/or glycerol with microorganisms adapted toproduce the isoprenoid compound, for example as described in U.S. Pat.No. 7,399,323. Methods of making the isoprenoid compounds as definedherein include chemical syntheses and biological syntheses andcombinations thereof in which suitable starting materials include forexample farnesene or farnesol or combinations thereof. Suitable methodsinclude methods in which farnesene, farnesol or combinations thereofhave been derived from biological sources, for example by treating asuitable feedstock with microorganisms to produce the farnesene and/orfarnesol, for example by treating a suitable feedstock withmicroorganisms adapted to produce the farnesene and/or farnesol, forexample as described in U.S. Pat. No. 7,399,323.

Methods of making the isoprenoid compounds as defined herein includechemical syntheses and biological syntheses and combinations thereof inwhich suitable starting materials include for example isoprenoidcompounds containing two isoprenyl units, for example geraniol, neroland citronellol and combinations thereof. Suitable methods includemethods in which the isoprenoid compound containing two isoprenyl unitshas been derived from biological sources, for example by treating asuitable feedstock with microorganisms to produce the isoprenoidcompound, for example by treating a suitable feedstock withmicroorganisms adapted to produce the isoprenoid compound.

In at least some examples of the present disclosure, the at least oneisoprenoid compound exhibits a Kv40 C (kinematic viscosity measured at40° C.) of 70 cSt or less, for example a Kv40 C of 50 cSt or less, or aKv40 C of 40 cSt or less, or a Kv40 C of 30 cSt or less, or a Kv40 C of20 cSt or less. In at least some examples of the present disclosure, theat least one isoprenoid compound exhibits a Kv100 C (kinematic viscositymeasured at 100° C.) of from 2 cSt to 18 cSt, for example Kv100 C offrom 2 cSt to 14 cSt, or a Kv100 C of from 2 cSt to 10 cSt, or a Kv100 Cof from 2 cSt to 8.5 cSt, or a Kv100 C of from 2 cSt to 8 cSt, or aKv100 C of from 2 cSt to 7 cSt, or a Kv100 C of from 2 cSt to 6 cSt, ora Kv100 C of from 2 cSt to 5 cSt.

In at least some examples of the present disclosure, the totalconcentration of isoprenoid compounds as defined herein in thelubricating composition of the present invention is at least 0.5 wt %based on the total weight of the lubricating composition. For example,the total concentration of isoprenoid compounds as defined herein may beat least 1 wt % of the total weight of the lubricating composition, orat least 5 wt %, or at least 10 wt %, or at least 20 wt %, or at least30 wt %, or at least 40 wt %, or at least 50 wt %, or at least 60 wt %,or at least 70 wt % of the total weight of the lubricating compositionas herein defined. In at least some examples of the present disclosure,the total concentration of isoprenoid compounds as defined herein in thelubricating composition of the present invention is up to 90 wt %, basedon the total weight of the lubricating composition. For example, thetotal concentration of isoprenoid compounds as defined herein may be upto 85 wt %, or up to 80 wt %, or up to 75 wt %, based on the totalweight of the lubricating composition.

The total concentration of isoprenoid compounds as defined herein in thebase stock is suitably at least 10 wt %, for example at least 20 wt %,at least 30 wt %, at least 40 wt %, at least 50 wt %, at least 60 wt %,at least 70 wt %, at least 80 wt % or at least 90 wt % based on thetotal weight of the base stock. In at least some examples of the presentdisclosure, the total concentration of isoprenoid compounds as definedherein, in the base stock is up to 95 wt %, for example up to 98 wt % orup to 99 wt %. Thus, the base stock may consist only of isoprenoidcompounds as defined herein.

In at least some examples, the base stock comprises two or moreisoprenoid compounds as defined herein, for example three or moreisoprenoid compounds as defined herein. For example, in at least someexamples, the base stock contains two or more isoprenoid compoundswherein the two or more isoprenoid compounds exhibit differentviscosity. Thus, the viscosity properties of the base stock may beadjusted.

In at least some examples of the present disclosure, the base stockexhibits a Kv40 C of 70 cSt or less, for example a Kv40 C of 50 cSt orless, or a Kv40 C of 40 cSt or less, or a Kv40 C of 30 cSt or less, or aKv40 C of 20 cSt or less.

In at least some examples of the present disclosure, the base stockexhibits a Kv100 C of from 2 cSt to 18 cSt, for example Kv100 C of from2 cSt to 14 cSt, or a Kv100 C of from 2 cSt to 10 cSt, or a Kv100 C offrom 2 cSt to 8.5 cSt, or a Kv100 C of from 2 cSt to 8 cSt, or a Kv100 Cof from 2 cSt to 7 cSt, or a Kv100 C of from 2 cSt to 6 cSt, or a Kv100C of from 2 cSt to 5 cSt.

In at least some examples the base stock is an aqueous base stock or isa non-aqueous base stock. Suitably, the base stock is a non-aqueous basestock.

In at least some examples, the base stock contains one or moreisoprenoid compounds as defined herein, wherein at least one of theisoprenoid compounds is derived from a biological source, for example bya microbiological process for conversion of sugar(s) or glycerol toisoprenoid compound/compounds by treatment with microorganisms, forexample by treatment with microorganisms adapted to produce theisoprenoid compound or precursor thereof. In particular examples, atleast one of the isoprenoid compounds is derived from a biologicalsource of farnesene or farnesol or combinations thereof.

In at least some examples the base stock contains at least 25% by weightbiobased carbon, for example at least 32% by weight biobased carbon orat least 47% by weight biobased carbon. In at least some examples thebase stock contains at least 25%, or at least 32% or at least 47%, byweight biobased carbon present as one or more isoprenoid compounds asdefined herein. Methods of measuring biobased carbon content includethose described in US Federal Register Vol. 78, no. 112 Tuesday June 11p 34867 7 CFR Part 3201 final rule including for example 3201.102,including for example as specified in the applicable section of subpartB of part 2902 and as defined in ASTM Method D6866 “Standard TestMethods for Determining the Biobased Content of Natural Range MaterialsUsing Radiocarbon and Isotope Ratio Mass Spectroscopy Analysis”.

In at least some examples, the base oil of lubricating viscosityadditionally comprises one or more base stocks other than the isoprenoidbase stocks defined herein. For example, base stocks suitable for use inthe base oil of the lubricating composition of the invention include oneor more additional basestock selected from Group I, Group II, Group III,Group IV and Group V base stocks, and mixtures thereof.

Thus, according to a further aspect of the present disclosure there isprovided a base oil for a lubricating composition which base oilcomprises a first base stock comprising or consisting of at least oneisoprenoid compound as defined herein and one or more additional basestocks selected from Group I, Group II, Group III, Group IV and Group Vbase stocks and mixtures thereof.

Suitable isoprenoid compounds in accordance with this aspect of thedisclosure include those described herein in relation to the lubricatingcompositions of the present invention.

Suitable first base stocks in accordance with this aspect of thedisclosure include base stocks comprising or consisting of at least oneisoprenoid compound described herein in relation to the lubricating oilcomposition of the present invention.

In at least some examples of the present disclosure the base oilcontains, at least 10 wt %, for example, at least 20 wt % of the basestock as defined herein, or at least 30 wt %, or at least 40 wt %, or atleast 50 wt %, or at least 60 wt %, or at least 70 wt %, or at least 80wt %, or at least 90 wt % of a base stock which comprises or consists ofat least one isoprenoid compound as herein defined. In at least someexamples of the present disclosure, the base oil comprises up to 95 wt%, for example up to 98 wt % or up to 99 wt % of the base stock asdefined herein.

In at least some examples the base oil contains at least 25% by weightbiobased carbon, for example at least 32% by weight biobased carbon orat least 47% by weight biobased carbon. In at least some examples thebase oil contains at least 25%, or at least 32% or at least 47%, byweight biobased carbon present as one or more isoprenoid compounds asdefined herein. Methods of measuring biobased carbon content includethose described in US Federal Register Vol. 78, no. 112 Tuesday June 11p 34867 7 CFR Part 3201 final rule including for example 3201.102,including for example as specified in the applicable section of subpartB of part 2902 and as defined in ASTM Method D6866 “Standard TestMethods for Determining the Biobased Content of Natural Range MaterialsUsing Radiocarbon and Isotope Ratio Mass Spectroscopy Analysis”.

In at least some examples of the present disclosure, the base oilexhibits a Kv40 C of 700 or less, for example, a Kv40 C of 50 or less ora Kv40 C of 40 or less, or a Kv40 C of 30 or less, or a Kv40 C of 20 orless.

In at least some examples of the present disclosure, the base oilexhibits a Kv100 C of from 2 to 18, for example Kv100 C of from 2 to 14,or a Kv100 of from 2 to 10, or a Kv100 C of from 2 to 8.5, or a Kv100 Cof from 2 to 8, or a Kv100 C of from 2 to 7, or a Kv100 C of from 2 to6, or a Kv100 C of from 2 to 5.

In at least some examples the base oil is an aqueous base oil or is anon-aqueous base oil. Suitably, the base oil is a non-aqueous base oil.

The lubricating composition of the invention suitably comprises a majoramount of base oil and a minor amount of one or more lubricantadditives. Major amount means at least 50% by weight, for examplegreater than 50% by weight. Minor amount means less than 50% by weight.

In another aspect, the present invention provides a method of preparinga lubricating composition as defined herein, comprising the step ofcombining a major amount of abase oil of lubricating viscosity and aminor amount of at least one lubricant additive, wherein the base oilcomprises or consists of a base stock comprising one or more isoprenoidcompounds as defined herein.

Major amount means at least 50% by weight, for example greater than 50%by weight. Minor amount means less than 50% by weight.

In at least some examples the lubricating composition is an aqueouslubricating composition or is a non-aqueous lubricating composition.Suitably, the lubricating composition is a non-aqueous lubricatingcomposition.

Suitable lubricant additives for the lubricating composition and/or forthe method of preparing a lubricating composition include detergents(including metallic and non-metallic detergents), friction modifiers,dispersants (including metallic and non-metallic dispersants), viscositymodifiers, dispersant viscosity modifiers, viscosity index improvers,pour point depressants, anti-wear additives, rust inhibitors, corrosioninhibitors, antioxidants (sometimes also called oxidation inhibitors),anti-foams (sometimes also called anti-foaming agents), seal swellagents (sometimes also called seal compatibility agents), extremepressure additives (including metallic, non-metallic, phosphoruscontaining, non-phosphorus containing, sulphur containing andnon-sulphur containing extreme pressure additives), surfactants,demulsifiers, anti-seizure agents, wax modifiers, lubricity agents,anti-staining agents, chromophoric agents, metal deactivators, andmixtures of two or more thereof.

In at least some examples, the at least one lubricant additive includesat least one detergent. Examples of detergents include ashlessdetergents (that is, non-metal containing detergents) andmetal-containing detergents. Suitable non-metallic detergents aredescribed for example in U.S. Pat. No. 7,622,431. Metal-containingdetergents comprise at least one metal salt of at least one organicacid, which is called soap or surfactant. Suitable organic acids includefor example, sulphonic acids, phenols (suitably sulphurised andincluding for example, phenols with more than one hydroxyl group,phenols with fused aromatic rings, phenols which have been modified forexample, alkylene bridged phenols, and Mannich base-condensed phenolsand saligenin-type phenols, produced for example by reaction of phenoland an aldehyde under basic conditions) and sulphurised derivativesthereof, and carboxylic acids including for example, aromatic carboxylicacids (for example hydrocarbyl-substituted salicylic acids andderivatives thereof, for example hydrocarbyl substituted salicylic acidsand sulphurised derivatives thereof).

In at least some examples, the at least one lubricant additive includesat least one friction modifier. Suitable friction modifiers include forexample, ash-producing additives and ashless additives. Examples ofsuitable friction modifiers include fatty acid derivatives including forexample, fatty acid esters, amides, amines, and ethoxylated amines.Examples of suitable ester friction modifiers include esters of glycerolfor example, mono-, di-, and tri-oleates, mono-palmitates andmono-myristates. A particularly suitable fatty acid ester frictionmodifier is glycerol monooleate. Examples of suitable friction modifiersalso include molybdenum compounds for example, organo molybdenumcompounds, molybdenum dialkyldithiocarbamates, molybdenumdialkylthiophosphates, molybdenum disulphide, tri-molybdenum clusterdialkyldithiocarbamates, non-sulphur molybdenum compounds and the like.Suitable molybdenum-containing compounds are described for example, inEP 1533362 A1 for example in paragraphs [0101] to [0117].

In at least some examples, the at least one lubricant additive includesat least one dispersant. Examples of suitable ashless dispersantsinclude oil soluble salts, esters, amino-esters, amides, imides andoxazolines of long chain hydrocarbon-substituted mono- andpolycarboxylic acids or anhydrides thereof; thiocarboxylate derivativesof long chain hydrocarbons; long chain aliphatic hydrocarbons containingpolyamine moieties attached directly thereto; Mannich condensationproducts formed by condensing a long chain substituted phenol withformaldehyde and polyalkylene polyamine; Koch reaction products and thelike.

In at least some examples, the at least one lubricant additive includesat least one dispersant viscosity modifiers. Examples of suitabledispersant viscosity modifiers and methods of making them are describedin WO 99/21902, WO2003/099890 and WO2006/099250.

In at least some examples, the at least one lubricant additive includesat least one viscosity index improver. Examples of suitable viscositymodifiers include high molecular weight hydrocarbon polymers (forexample polyisobutylene, copolymers of ethylene and propylene and higheralpha-olefins); polyesters (for example polymethacrylates); hydrogenatedpoly(styrene-co-butadiene or isoprene) polymers and modifications (forexample star polymers); and esterified poly(styrene-co-maleic anhydride)polymers. Oil-soluble viscosity modifying polymers generally exhibitnumber average molecular weights of at least 15000 to 1000000,preferably 20000 to 600000 as determined by gel permeationchromatography or light scattering methods.

In at least some examples, the at least one lubricant additive includesat least one pour point depressant. Examples of suitable pour pointdepressants include C₈ to C₁₈ dialkyl fumarate/vinyl acetate copolymers,methacrylates, polyacrylates, polyarylamides, polymethacrylates,polyalkyl methacrylates, vinyl fumarates, styrene esters, condensationproducts of haloparaffin waxes and aromatic compounds, vinyl carboxylatepolymers, terpolymers of dialkyfumarates, vinyl esters of fatty acidsand allyl vinyl ethers, wax naphthalene and the like.

In at least some examples, the at least one lubricant additive includesat least one anti-wear additive. Examples of suitable anti-wearadditives include non-phosphorus containing additives for example,sulphurised olefins. Examples of suitable anti-wear additives alsoinclude phosphorus-containing antiwear additives. Examples of suitableashless phosphorus-containing anti-wear additives include trilaurylphosphite and triphenylphosphorothionate and those disclosed inparagraph [0036] of US2005/0198894. Examples of suitable ash-forming,phosphorus-containing anti-wear additives include dihydrocarbyldithiophosphate metal salts. Examples of suitable metals of thedihydrocarbyl dithiophosphate metal salts include alkali and alkalineearth metals, aluminium, lead, tin, molybdenum, manganese, nickel,copper and zinc. Particularly suitable dihydrocarbyl dithiophosphatemetal salts are zinc dihydrocarbyl dithiophosphates (ZDDP).

In at least some examples, the at least one lubricant additive includesat least one rust inhibitor. Examples of suitable rust inhibitorsinclude non-ionic polyoxyalkylene polyols and esters thereof,polyoxyalkylene phenols, polyoxyalkylene polyols, anionic alky sulphonicacids, zinc dithiophosphates, metal phenolates, basic metal sulphonates,fatty acids and amines.

In at least some examples, the at least one lubricant additive includesat least one corrosion inhibitor. Examples of corrosion inhibitorsinclude phosphosulphurised hydrocarbons and the products obtained by thereaction of phosphosulphurised hydrocarbon with an alkaline earth metaloxide or hydroxide, non-ionic polyoxyalkylene polyols and estersthereof, polyoxyalkylene phenols, thiadiazoles, triazoles and anionicalkyl sulphonic acids. Examples of suitable epoxidised ester corrosioninhibitors are described in US2006/0090393.

In at least some examples, the at least one lubricant additive includesat least one antioxidant. Examples of suitable antioxidants includealkylated diphenylamines, N-alkylated phenylenediamines,phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamines,dimethylquinolines, trimethyldihydroquinolines and oligomericcompositions derived therefrom, hindered phenolics (including ashless(metal-free) phenolic compounds and neutral and basic metal salts ofcertain phenolic compounds), aromatic amines (including alkylated andnon-alkylated aromatic amines), sulphurised alkyl phenols and alkali andalkaline earth metal salts thereof, alkylated hydroquinones,hydroxylated thiodiphenyl ethers, alkylidenebisphenols, thiopropionates,metallic dithiocarbamates, 1,3,4-dimercaptothiadiazole and derivatives,oil soluble copper compounds (for example, copper dihydrocarbyl thio- orthio-phosphate, copper salts of a synthetic or natural carboxylic acids,for example a C₈ to C₁₈ fatty acid, an unsaturated acid or a branchedcarboxylic acid, for example basic, neutral or acidic Cu^(I) and/orCu^(II) salts derived from alkenyl succinic acids or anhydrides),alkaline earth metal salts of alkylphenolthioesters, suitably containingC₅ to C₁₂ alkyl side chains, calcium nonylphenol sulphide, bariumt-octylphenyl sulphide, dioctylphenylamine, phosphosulphised orsulphurised hydrocarbons, oil soluble phenates, oil soluble sulphurisedphenates, calcium dodecylphenol sulphide, phosphosulphurisedhydrocarbons, sulphurised hydrocarbons, phosphorus esters, low sulphurperoxide decomposers and the like.

In at least some examples, the at least one lubricant additive includesat least one antifoam. Examples of suitable anti-foam agents includesilicones, organic polymers, siloxanes (including poly siloxanes and(poly) dimethyl siloxanes, phenyl methyl siloxanes), acrylates and thelike.

In at least some examples, the at least one lubricant additive includesat least one seal swell agent. Examples of suitable seal swell agentsinclude long chain organic acids, organic phosphates, aromatic esters,aromatic hydrocarbons, esters (for example butylbenzyl phthalate) andpolybutenyl succinic anhydride.

According to the US Federal Register Vol. 78, no. 112 Tuesday June 11 p34867 7 CFR Part 3201 final rule for example 3201.102, engine crankcaseoil (that is lubricating compositions suitable for lubricating internalcombustion engine crankcases) may be designated with a biopreferredecolabel if they contain at least 25% by weight biobased carbon andwater turbine bearing oils may be designated with a biopreferredecolabel if they contain at least 46% by weight biobased carbon.

A base oil that contains at least 32% by weight biobased carbon willproduce a lubricating composition containing at least 25% by weightbiobased carbon when prepared to contain 20% by weight lubricantadditives. A base oil that contains at least 47% by weight biobasedcarbon will produce a lubricating composition containing at least 46% byweight biobased carbon when prepared to contain 2% by weight lubricantadditives.

In at least some examples the lubricating composition contains at least25% by weight biobased carbon, for example at least 32% by weightbiobased carbon or at least 46% by weight biobased carbon. In at leastsome examples the lubricating composition contains at least 25%, or atleast 32% or at least 46%, by weight biobased carbon present as one ormore isoprenoid compounds as defined herein. In at least some examplesthe lubricating composition is a crankcase lubricating oil and containsat least 25% by weight biobased carbon, for example present as one ormore isoprenoid compounds as defined herein. In at least some examplesthe lubricating composition is a water turbine bearing oil and containsat least 46% by weight biobased carbon, for example present as one ormore isoprenoid compounds as defined herein. Methods of measuringbiobased carbon content include those described in US Federal RegisterVol. 78, no. 112 Tuesday June 11 p 34867 7 CFR Part 3201 final ruleincluding for example 3201.102, including for example as specified inthe applicable section of subpart B of part 2902 and as defined in ASTMMethod D6866 “Standard Test Methods for Determining the Biobased Contentof Natural Range Materials Using Radiocarbon and Isotope Ratio MassSpectroscopy Analysis”.

According to another aspect of the present disclosure there is provideda method of lubricating a surface which comprises applying to saidsurface a lubricating composition as herein defined and/or prepared by amethod as herein defined.

Suitable surfaces include those in power transmission systems forexample drive lines and gear boxes for example for vehicles includingfor example passenger vehicles and heavy duty vehicles; and those ininternal combustion engines, for example the crankcases of internalcombustion engines. Suitable surfaces also include those in turbinebearings for example in water turbine bearings.

Suitable internal combustion engines include, for example, engines usedin automotive applications, engines used in marine applications andengines used in land-based power generation plants.

In at least some examples, the lubricating composition of the inventionis used to lubricate the crankcase of an internal combustion engine atany temperature which is typically encountered in an engine environment,for example a temperature in the range of ambient to 250° C., e.g. 90 to120° C. Typically, ambient temperature is 20° C., but according to atleast some embodiments, ambient temperature is for example less than 20°C., for example 0° C.

In a further aspect, the present invention provides the use as acomponent of a base stock for a lubricating composition of at least oneisoprenoid compound comprising:

(i) one or two oxygen-containing moieties independently selected fromether and ester moieties;

(ii) a first acyclic isoprenoid moiety containing 1 to 5 isoprenylunits; and

(iii) optionally, a second acyclic isoprenoid moiety containing 1 to 5isoprenyl units with the proviso that at least one isoprenoid moietycontains 3 to 5 isoprenyl units where the isoprenoid compound contains asingle ether moiety.

Suitable isoprenoid compounds in accordance with this aspect of theinvention include those described herein in relation to the base stocks,base oils or lubricating compositions of the invention. Thus, in atleast some examples the at least one isoprenoid compound is selectedfrom the compounds represented by formulae (1) to (8) described herein.Suitable compounds represented by formulae (1) to (8) that are describedherein in relation to the base stocks, base oils or lubricatingcompositions of the invention are also suitable in accordance with thisaspect of the invention.

Suitable base stocks include those described herein including aqueousbase stocks and non-aqueous base stocks. Suitably, the base stock is anon-aqueous base stock.

The present invention will now be described by reference to thefollowing examples. The examples are merely illustrative and shall notbe interpreted as in any way limiting the scope of protection as definedin the claims.

EXAMPLE 1 Synthesis of n-Alkyl Ethers of Farnesene Represented byFormula (9)

Alkyl ethers of farnesene represented by formula (9) were prepared bydissolving the n-alkyl alcohol (1 eq.) in tetrahydrofuran (15 vol. eq.)and warming to 30° C. to aid dissolution. Sodium hydride (1.5 eq.) wasadded portion wise to the solution over 15 minutes. The reaction mixturewas then warmed to reflux and stirred for 30 minutes. Farnesyl bromide(1 eq.) was then added over 15 minutes maintaining reflux. The reactionmixture was held at reflux for greater than 5 hours or overnight. Thereaction mixture was quenched onto saturated aqueous ammonium chloridesolution and extracted into ethyl acetate. The ethyl acetate extractswere combined and washed with brine. The extract was dried with MgSO₄,filtered through celite and concentrated to dryness giving, a yellowoil, which solidified on cooling. The crude product was purified bypassing through a silica plug eluted with 50% DCM (dichloromethane) inheptanes to give a colourless liquid after solvent removal.

EXAMPLE 2 Synthesis of Hydrogenated n-Alkyl Ethers of FarneseneRepresented by Formula (10)

The ether produced according to the procedure of Example 1 (1 eq.) wascharged to an autoclave with heptane (10 vol. eq.) and 5% Pt/C (10 wt%). The autoclave was sealed, placed in an ice water bath and thecontents stirred. When the contents had cooled to 5° C. the autoclavewas charged with hydrogen (20 atm). The reaction was allowed to warmslowly to room temperature overnight. ¹H NMR analysis of the reactionshowed that starting material had been consumed. The reaction mixturewas filtered through celite washing the filter-cake with heptane. Theheptane mother liquors were concentrated to give a crude productcontaining some cleaved ether by-products. Purification was performedusing silica chromatography to obtain a colourless liquid productcomprising hydrogenated n-alkyl ether of farnesene as represented byformula (10).

EXAMPLE 3 Synthesis of Farnesyl Oleate (12)

Farnesyl oleate which may be represented by formula (12), was preparedfrom oleic acid via conversion of oleic acid to the corresponding acidchloride and reaction with farnesol. Oleic acid (1 eq) was dissolved intoluene and warmed to 70-80° C. Thionyl chloride (1.5 eq.) was addeddrop wise to the reaction mixture over 30 minutes. The reaction mixturewas held at 70-80° C. for 3 hours and then cooled. Toluene and excessthionyl chloride were removed under vacuum to provide the crude acidchloride in quantitative yield. The crude acid chloride (1.2 eq.) wasdissolved in toluene. and a solution of farnesol (1.0 eq.) andtriethylamine (1.5 eq.) in toluene was added over 30 minutes. Thereaction mixture was stirred at 40° C. for 3 hours. In process ¹H NMRanalysis showed virtually all the farnesol had been consumed and anester had formed. The reaction mixture was allowed to cool to roomtemperature and then quenched into water. Brine was added to aidseparation of the aqueous and organic layers. The toluene layer wascollected, dried with MgSO₄ and concentrated to give the crude productas a yellow liquid. Impurities were removed by eluting through a silicagel plug with hexane then 5% dichloromethane in hexane to give acolourless liquid after removal of solvents.

EXAMPLE 4 Synthesis of Difarnesyl Ether (13)

Difarnesyl ether which may be represented by formula (13), was preparedby reaction of farnesol with farnesyl bromide in the presence of sodiumhydride and tetrahydrofuran solvent. Farnesol (1.0 eq.) was dissolved intetrahydrofuran and 60% sodium hydride (1.5 eq.) was added over 15minutes. The mixture was warmed to 50° C. and stirred for 30 minutes.86% Farnesyl bromide (1.0 eq.) was added over 10 minutes and stirred at50° C. overnight. The reaction was quenched into aqueous ammoniumchloride solution and extracted into ethyl acetate. The extracts werewashed with brine and concentrated to give a crude product. The crudematerial was purified by passing through a silica plug to give acolourless oil after removal of solvents.

EXAMPLE 5 Synthesis of Hydrogenated Difarnesyl Ether (14)

The hydrogenated difarnesyl ether which may be represented by formula(14) was produced by hydrogenating the ether prepared according to theprocedure of Example 4 (1 eq.) by charging it to an autoclave withheptane (10 vol. eq.) and 5% Pt/C (10 wt %). The autoclave was sealed,placed in an ice water bath and the contents stirred. When the contentshad cooled to 5° C. the autoclave was charged with hydrogen (10 atm).The reaction was allowed to warm slowly to room temperature overnight.¹H NMR analysis of the reaction showed that starting material had beenconsumed. The reaction mixture was filtered through celite washing thefilter-cake with heptane. The heptane mother liquors were concentratedto give a crude product containing some cleaved ether by-products.Purification was performed using silica chromatography to obtain acolourless liquid product.

EXAMPLE 6 Synthesis of furan-2,5-dicarboxylic acid difarnesyl ester (21)

Furan-2,5-dicarboxylic acid difarnesyl ester (also calleddifarnesyl-furan-2,5-dicarboxylate), which is a diester which may berepresented by formula (21), was prepared via conversion offuran-2,5-dicarboxylic acid to the corresponding diacid chloridefollowed by reaction with farnesol. Furan-2,5-dicarboxylic acid (1 eq.)was slurried in toluene (10 vol. eq.) and thionyl chloride (2.5 eq.),dimethyl formamide (0.05 eq) was added and the mixture was heated to 80°C. overnight. When ¹H NMR analysis showed that the reaction had gone tocompletion, the reaction mixture was concentrated under vacuum toprovide the diacid chloride as an off-white solid. The diacid chloride(1.0 eq) was dissolved in toluene (10.) without further purification,and a solution of farnesol (2.0 eq.) in toluene (10.) and triethylamine(2.5 eq.) was added over 30 minutes. Ice/water cooling was applied tomaintain the reaction temperature at 30° C. The reaction mixture wasthen stirred at 25° C. for 2 hours. When ¹H NMR analysis showed thatesterification was complete, the reaction mixture was quenched intobrine and the product extracted into toluene. The toluene extracts weredried with MgSO₄, filtered through celite and concentrated to dryness.The crude product was then purified by passing through a silica plug andeluting with 75% dichloromethane in hexane to provide a colourlessliquid product.

EXAMPLE 7 Hydrogenated furan-2,5-dicarboxylic acid difarnesyl ester (22)

The hydrogenated diester (hydrogenated furan-2,5-dicarboxylic aciddifarnesyl ester also called hydrogenateddifarnesyl-furan-2,5-dicarboxylate) which may be represented by formula(22) was prepared by hydrogenation. The diester represented by formula(21) (1 eq.) which had been produced according to the procedure ofExample 6, was charged to an autoclave with ethyl acetate (10.) and 5%Pt/C (10 wt %). The autoclave was sealed, charged with hydrogen (20atm), and stirred overnight at room temperature. ¹H NMR analysis of thereaction showed that starting material had been consumed. The reactionmixture was filtered through celite washing the filter-cake with ethylacetate. The ethyl acetate mother liquors were concentrated to give acrude product containing some cleaved ether by-products. Purificationwas performed using silica chromatography to obtain a colourless liquidproduct.

EXAMPLE 8 Synthesis of Hydrogenated Difarnesyl Terephthalate (23)

Hydrogenated difarnesyl terephthalate (also called hydrogenateddifarnesyl terephthalate) which may be presented by formula (23) wasprepared by the reaction of hydrogenated farnesol with terephthaloylchloride. Terephthaloyl chloride (1.0.eq.) was dissolved indichloromethane with excess triethylamine, excess hydrogenated farnesoland pyridine, and the resulting mixture was heated to reflux overnight.After removal of solvents, the crude material was purified by flashchromatography with heptanes to give a 3:2 mixture of difarnesylterephthalate (23) and hydrogenated farnesene (by GC). The mixture wasdistilled under vacuum to remove the alkane to provide the difarnesylterephthalate product as a yellow liquid.

EXAMPLE 9 Synthesis of Compound Represented by Formulae (11) and (19)

The compound represented by formula (19)

was produced, it is believed, during the acid catalysed formation of acompound represented by formula (11):

It is believed that this material is a mixture of isomers with differentconnectivity which is non-terminal. This is supported by proton NMRanalysis. This conclusion is based upon the evidence that the viscosityof the mixture resulting from the reaction is appreciably thicker thanthe mono-ether that was formed. The method of preparation was:

Farnesene (40.8 g, 20.0 mmol, 1.0 eq) was combined with lauryl alcohol(37.2 g, 20.0 mmol, 1.0 eq.) and Ambelyst 15 (4.08 g, 10 wt %). Themixture was heated to 65° C. and stirred overnight. The reaction mixturewas diluted with heptane (200 mL) and filtered through celite. Thiscrude reaction mixture was hydrogenated in the presence of 5% Pt/Ccatalyst under an atmosphere of hydrogen (30 atm) initially 0° C.-20° C.and then 50° C. to drive the reduction to completion. The reactionmixture was filtered through celite and concentrated to give acolourless oil 75 g. The crude product was placed under a high vacuum(<1 mbar), and heated in an oil bath to remove any volatile materials(180° C. head temp). After all volatiles were removed 20.0 g of residueremained as a colourless oil (25.6% yield over two chemistry steps).

EXAMPLE 10 Properties of Isoprenoid Compounds

Isoprenoid compounds of formulae (9) to (23) were tested for thefollowing key lubricant properties:

-   -   Kinematic viscosity at 40° C. and 100° C. (ASTM D445)    -   Viscosity Index (ASTM D2270)    -   Pour Point (ASTM D7346)    -   Volatility (IP 393: Determination of volatility of automotive        lubricating oils—Thermo-Gravimetric method)

The Thermo-Gravimetric Analysis simulation of the traditional Noack testwas conducted due to limited sample available for testing (thetraditional Noack test requires around 50 ml of sample). 15 mg of samplewas loaded into a platinum sample pan and suspended from amicro-balance. The suspended pan containing the sample was thenpositioned inside a furnace and heated at a constant rate under flowingnitrogen gas. The result was calculated relative to a reference oil ofknown volatility that was run before and after the sample. For example,a reference compound of Noack volatility 12.5% is heated and thetemperature at which its mass falls to 87.5% recorded. The target samplewas then analysed to determine its mass loss at this temperature.

The results are shown in Table 2 (optimum values are included inparentheses) together with comparative results obtained using SKYubase 4(a commercially-available Group III base stock).

TABLE 2 Compound Pour TGA represented KV100/ KV40/ Point/ Noack/ byformula: cSt cSt VI ° C. %  9 (n = 10) 2.4 6.6 202 −45 20  9 (n = 12)2.7 8.2 202 −24 10  9 (n = 16) 3.7 16 124 6 5 10 (n = 10) 2.8 9.4 155−39 20 10 (n = 12) 3.7 14 156 −18 6 10 (n = 16) 4.2 17 167 9 3 12 3.8 14182 −30 3 13 2.7 10 116 −81 26 14 3.5 14 131 −75 12 21 8.9 63 116 −45 59(decomposed) 22 6.3 38 116 −54 5 23 9.2 70 106 −48 2 Yubase 4 4.2 19 125−15 13

These results demonstrate that all of the tested compounds exhibitkinematic viscosity values that make them potentially suitable forblending into automotive crankcase lubricants. All of the testedcompounds exhibit viscosity indexes in the target range (>100) and manyexhibit viscosity indexes above 140.

Most of the tested compounds exhibit pour points below −10° C., and manyexhibit pour points in a preferred range below −25° C. For formulationinto lubricants, pour point depressants may be used to adjust the pourpoint if necessary. In general, the pour point was found to increasewith saturation.

Volatility measured by simulated Noack on TGA gave good results for mostcompounds, especially compared to conventional base oils of comparableviscosity. The high value for compound 21 is attributed to thermaldecomposition of the material during the test, rather than a truemeasurement of volatility.

The tested compounds all compare favourably with Yubase 4.

Generally, the data support an observation that isoprenoid compoundswith saturated isoprenoid moieties exhibit longer oxidative inductiontimes and/or higher oxidation ignition temperatures. Thus, thesecompounds are generally more oxidative stable.

EXAMPLE 11 Aniline Point

The aniline point of each compound of formula (10) [n=10] and (14) wasdetermined according to ASTM D611. The aniline point is an indication ofthe polarity of the compounds and their propensity to cause sealswelling. Lower values indicate that the material is more polar and morelikely to cause significant swelling of elastomeric seals. The resultsare shown in Table 3, together with comparative results obtained forYubase 4.

TABLE 3 Compound Aniline Mixed Aniline represented Point/ Point/ byformula: ° C. ° C. 10 (n = 10) 82.2 74.3 14 99.3 88.5 Yubase 4 116.095.2

The results obtained compare favourably with Yubase 4, and suggest thatthe compounds will not cause seal swelling problems.

EXAMPLE 12 Deposit Testing

The TEOST MHT deposit bench test (ASTM D 7097) is designed to predictthe deposit forming tendencies of engine oil in the piston ring belt andupper piston crown area. The test was run in duplicate on a formulatedengine oil comprising 50 wt % of test compound, 10.21 wt % of anadditive pack, 0.5 wt % of anti-wear additive, 6 wt % of viscositymodifier, 32.99 wt % of Yubase 4, and 0.2 wt % of pour point depressant.

The additive pack composition contained dispersant, calcium sulphonateand phenate detergents, antioxidants and anti-foam.

The results are shown in Table 4, together with comparative resultsobtained for a lubricating composition with all the base oil beingYubase 4.

TABLE 4 Compound Test 1 Test 2 Average represented Deposits/ Deposits/Deposits/ by formula: mg mg mg 10 (n = 10) 65.5 65.1 65.3 14 58.3 65.161.7 Yubase 4 84.8 80.8 82.8

The test compounds significantly outperformed Yubase 4, demonstratingvery low deposit forming tendency of the test compounds.

EXAMPLE 13 High Temperature Corrosion Bench Test (HTCBT)

The test was run in accordance with ASTM D6594, which evaluates thecorrosiveness of diesel engine oil at 135° C. and is intended tosimulate the corrosion process of non-ferrous metals exposed to engineoil. For instance, copper is present in the engine turbo bearings andoil cooler, whilst lead is present in the bearings of an engine.

The test was run on a formulated engine oil comprising 50 wt % of testcompound, 10.21 wt % of an additive pack, 0.5 wt % of anti-wearadditive, 6 wt % of viscosity modifier, 32.99 wt % of Yubase 4, and 0.2wt % of pour point depressant.

The additive pack composition contained dispersant, calcium sulphonateand phenate detergents, antioxidants and anti-foam.

As part of the test, four metal coupons were immersed in hot oil (135°C.) for a period of seven days. At the end of this period, the levels oftest metals dissolved in the oil were measured. The pass criteria forthe HTCBT test is: Cu<20 ppm; Pb<120 ppm; copper strip rating of <3.

The results, including kinematic viscosity (ASTM D445) and total basenumber (TBN) measurements for the test oils following completion of thetest, are shown in Table 5, together with comparative results obtainedfor a lubricating composition with all the base oil being Yubase 4.

TABLE 5 Compound TBN represented Copper/ Lead/ Tin/ Copper KV40 % KV100% D4739 by formula: ppm ppm ppm rating change change change 10 (n = 10)3 40 0 1b −3 −2 −0.9 14 3 38 0 1b −4 −4 −0.6 Yubase 4 3 10 0 1b −5 −3−1.1

The results obtained compare favourably with Yubase 4; the testcompounds passed each of the test criteria, suggesting that thecompounds will not cause corrosion problems.

EXAMPLE 14 Seals Testing

This test was run in accordance with industry standard method CEC L39-T-96, except that, due to limited sample availability, only 100 g ofoil (as opposed to 270 g used in the standard method) was used fortesting.

The test was run on a formulated engine oil comprising 50 wt % of testcompound, 10.21 wt % of an additive pack, 0.5 wt % of anti-wearadditive, 6 wt % of viscosity modifier, 32.99 wt % of Yubase 4, and 0.2wt % of pour point depressant.

The additive pack composition contained dispersant, calcium sulphonateand phenate detergents, antioxidants and anti-foam.

As part of the test, an ethylene acrylate rubber seal was immersed inthe test oil for 168 hours at elevated temperature.

The results are shown in Table 6, together with comparative resultsobtained for a lubricating composition with all the base oil beingYubase 4. Lower and upper limit pass criteria of the test are alsoincluded in Table 6.

TABLE 6 Compound Tensile Elongation Volume represented Strength/Rupture/ variation/ by formula: % % Hardness % Pass limits −15/18 −35/10−5/8 −7/5 (lower/upper) 12 1.7 −10.3 −4.6 4.7 10 (n = 10) 7.8 −24.8 0.81.0 14 −2.4 −29.0 5.9 1.3 Yubase 4 −1.3 −27.9 1.6 0.4

The results obtained compare favourably with Yubase 4; the testcompounds passed each of the test criteria, suggesting that thecompounds will not cause seal swelling problems.

EXAMPLE 15 Volatility Testing

The test was run in accordance with IP 393 (Determination of volatilityof automotive lubricating oils—Thermo-Gravimetric method). TheThermo-Gravimetric Analysis simulation of the traditional Noack test wasconducted substantially as reported in Example 10 using 15 mg samples.The test was run in duplicate on a formulated engine oil comprising 5 wt% of test compound, 10.21 wt % of an additive pack, 0.5 wt % ofanti-wear additive, 6 wt % of viscosity modifier, 77.99 wt % of Yubase4, and 0.3 wt % of pour point depressant.

The results are shown in Table 7 together with comparative resultsobtained using a formulated engine oil comprising 10.21 wt % of anadditive pack, 0.5 wt % of anti-wear additive, 6 wt % of viscositymodifier, 82.99 wt % of Yubase 4, and 0.3 wt % of pour point depressant.Table 7 also includes results for kinematic viscosity measurements (ASTMD445) for the test oils.

TABLE 7 Compound TGA represented KV40/ KV100/ Noack/ by formula: cSt cSt% 10 (n = 10) 51.15 9.52 14.2 10 (n = 12) 48.96 9.31 12.1 10 (n = 16)49.27 9.33 21.1 Yubase 4 50.9 9.4 12.5

Volatility measured by simulated Noack on TGA gave good results for thetest compounds, which compare favourably with Yubase 4. Moreover, theresults of the test demonstrate that even at a low treat rate of 5 wt %,the test compounds provide oils with desirably low viscosity, withoutdetrimentally impacting upon oil volatility. Thus, advantageously, testcompounds can be used even at low concentrations to provide engine oilsof both low viscosity and low volatility.

These results demonstrate that the tested compounds exhibit properties,for example kinematic viscosity values, that make them suitable for useas a component of a base stock for a lubricating composition and forblending into lubricating compositions suitable for use in a method oflubricating the crankcase of an internal combustion engine. Suchlubricating compositions may be prepared by a method comprising the stepof combining a major amount of a base oil of lubricating viscosity and aminor amount of at least one lubricant additive, wherein the base oilcomprises or consists of a basestock as herein defined. Major amountmeans at least 50% by weight, for example greater than 50% by weight.Minor amount means less than 50% by weight.

What is claimed is: 1-21. (canceled)
 22. A lubricating compositioncomprising a base oil of lubricating viscosity and one or more lubricantadditives, wherein the base oil comprises or consists of a base stockwhich comprises or consists of at least one isoprenoid compoundcomprising: (i) one or two oxygen-containing moieties independentlyselected from ether and ester moieties; (ii) a first acyclic isoprenoidmoiety containing 1 to 5 isoprenyl units; and (iii) optionally, a secondacyclic isoprenoid moiety containing 1 to 5 isoprenyl units with theproviso that at least one isoprenoid moiety contains 3 to 5 isoprenylunits where the isoprenoid compound contains a single ether moiety. 23.A lubricating composition according to claim 23 wherein the isoprenoidcompound comprises: (i) one or two oxygen-containing moietiesindependently selected from ether and ester moieties; (ii) a firstacyclic isoprenoid moiety containing 3 to 5 isoprenyl units; and (iii)optionally, a second acyclic isoprenoid moiety containing 1 to 5isoprenyl units.
 24. A lubricating composition according to claim 23,wherein the isoprenoid compound is represented by the formula (1), (2)or (3):R¹—O-T¹  (1)R²—C(O)O-T²  (2)T³-O-T⁴  (3) wherein: R¹ and R² each represent an acyclic unsubstitutedhydrocarbyl group or an acyclic substituted hydrocarbyl group other thanan acyclic, saturated or unsaturated, isoprenoid moiety containing from1 to 5 isoprenyl units; T¹ represents an acyclic, saturated orunsaturated, isoprenoid moiety containing from 3 to 5 isoprenyl units;T² represents an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 1 to 5 isoprenyl units; and T³ and T⁴ each represent anacyclic, saturated or unsaturated, isoprenoid moiety containing from 1to 5 isoprenyl units, with the proviso that at least one of T³ and T⁴represents an acyclic, saturated or unsaturated, isoprenoid moietycontaining from 3 to 5 isoprenyl units.
 25. A lubricating compositionaccording to claim 22, wherein the isoprenoid compound is represented bythe formula (4), (5), (6), (7) or (8):R³—O—R⁴—O-T⁵  (4)T⁶-O—R⁵—O-T⁷  (5)R⁶—O-T⁸-O—R⁷  (6)R⁸—OC(O)—R⁹—C(O)O-T⁹  (7)T¹⁰-OC(O)—R¹⁰—C(O)O-T¹¹  (8) wherein: R³, R⁶, R⁷ and R⁸ eachindependently represent an acyclic unsubstituted hydrocarbyl group or anacyclic substituted hydrocarbyl group other than an acyclic, saturatedor unsaturated, isoprenoid moiety containing from 1 to 5 isoprenylunits; R⁴ and R⁵ each independently represent a divalent, cyclic oracyclic hydrocarbyl group, other than a divalent acyclic, saturated orunsaturated, isoprenoid moiety containing from 1 to 5 isoprenyl units;or a heterocyclyl group; R⁹ and R¹⁰ each independently represent adivalent, cyclic or acyclic hydrocarbyl group, other than a divalentacyclic, saturated or unsaturated, isoprenoid moiety containing from 1to 5 isoprenyl units; a heterocyclyl group; or a covalent bond; T⁸represents a divalent acyclic, saturated or unsaturated, isoprenoidmoiety containing from 1 to 5 isoprenyl units; and T⁵, T⁶, T⁷, T⁹, T¹⁰and T¹¹ each independently represents an acyclic, saturated orunsaturated, isoprenoid moiety containing from 1 to 5 isoprenyl units.26. A lubricating composition according to claim 24, wherein T¹, T², T³,T⁴, T⁵, T⁶, T⁷, T⁹, T¹⁰, and T¹¹ each independently represents anacyclic, saturated or unsaturated, isoprenoid moiety containing 3, 4 or5 isoprenyl units.
 27. A lubricating composition according to claim 25,wherein T¹, T², T³, T⁴, T⁵, T⁶, T⁷, T⁹, T¹⁰, and T¹¹ each independentlyrepresents an acyclic, saturated or unsaturated, isoprenoid moietycontaining 3, 4 or 5 isoprenyl units
 28. A lubricating compositionaccording to claim 25, wherein T⁸ represents a divalent acyclic,saturated or unsaturated, isoprenoid moiety containing 3, 4 or 5isoprenyl units.
 29. A lubricating composition according to claim 22,wherein the at least one isoprenoid compound exhibits a Kv40 C of 70 cStor less.
 30. A lubricating composition according to claim 22, whereinthe at least one isoprenoid compound exhibits a Kv100 C of from 2 cSt to18 cSt.
 31. A lubricating composition according to claim 22, wherein thebase stock comprises at least 10 wt % of the at least one isoprenoidcompound.
 32. A lubricating composition according to claim 22, whereinthe base stock exhibits a Kv40 C of 70 cSt or less.
 33. A lubricatingcomposition according to claim 22, wherein the base stock exhibits aKv100 C in the range of 2 to 18 cSt.
 34. A lubricating compositionaccording to claim 22, wherein the base oil further comprises one ormore additional base stocks selected from the group consisting of GroupI, Group II, Group III, Group IV and Group V base stocks, and mixturesthereof.
 35. A base oil for a lubricating composition which base oilcomprises a first base stock comprising or consisting of at least oneisoprenoid compound as defined in claim 22 and one or more additionalbase stocks selected from the group consisting of Group I, Group II,Group III, Group IV and Group V base stocks and mixtures thereof.
 36. Abase oil according to claim 35 which base oil exhibits a Kv40 C of 70cSt or less.
 37. A base oil according to claim 35 which base oilexhibits a Kv100 C in the range of 2 to 18 cSt.
 38. A base oil accordingto claim 35, wherein the first base stock comprises at least 10 wt % ofthe at least one isoprenoid compound.
 39. A method of preparing alubricating composition as defined in claim 22, which method comprisesthe step of combining a major amount of a base oil of lubricatingviscosity and a minor amount of at least one lubricant additive, whereinthe base oil comprises or consists of a base stock comprising the atleast one isoprenoid compound.
 40. A method according to claim 39wherein the base oil comprises at least 10 wt % of the at least oneisoprenoid compound.
 41. A method according to claim 40 wherein the baseoil is a base stock which comprises or consists of the at least oneisoprenoid.
 42. A method of lubricating a surface which comprisesapplying to said surface a lubricating composition according to claim22.